Polymer 1D photonic crystals

ABSTRACT

A multilayer nonlinear dielectric optical structure is formed by coextruding at least two polymeric materials, components (a) and (b), using a multiplying element; the structure contains a plurality of alternating layers (A) and (B) represented by formula (AB) x , where x=2 n , and n is the number of multiplying elements; at least one of the components (a) and (b) exhibits nonlinear optical response. These structures perform a variety of nonlinear optical functions including all-optical switching and passive optical limiting.

This application is a continuation of application Ser. No. 09/794,492,filed Feb. 28, 2001 now U.S. Pat. No. 6,582,807 issued Jun. 24, 2003;application Ser. No. 09/794,492 claims priority to U.S. Provisionalpatent application Serial No. 60/195,697, filed Apr. 7, 2000, both ofwhich are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the materials and a method for fabricatingmultilayer nonlinear dielectric optical structures from polymericmaterials. In particular, the present invention relates to multilayermaterials characterized by a modulation in the nonlinear refractiveindex in the direction normal to the surface of the layers.

2. Discussion of the Related Art

The propagation of electromagnetic waves through periodic structuresconsisting of layers of materials with an intensity-dependent dielectricconstant has been studied both theoretically and experimentally. Ahistorical review was reported by Brown et al ( T. G. Brown and B. J.Eggleton, Optics Express 3, 385 (1998)). The transmission and reflectionproperties of such structures are strongly modulated by the intensity ofthe incident light. The optical response of such structures can includeoptical switching, optical limiting, optical bistability and someremarkable pulse propagation effects including transverse patternformation.

Some optical effects have been shown experimentally using, for example,colloidal arrays (C. Herbert and M. Malcuit.; Opt. Lett. 17, 1037(1992)), semiconductor multilayers, silicon-on-insulator waveguides (N.D. Sankey, D. F. Prelewitz and T. G. Brown; Appl. Phys Lett. 60, 1427(1992)) and fiber gratings (S. Larochelle, Y. Hibino, V. Mizrahi and G.Stegeman; Electron. Lett. 26, 1459 (1990)). An organic nonlineardielectric stack was reported by Norwood et al. in 1992 using a siliconnaphthalocyaine-poly(methyl methacrylate) structure made by spin coatingsequential layers (R. A. Norwood et al.; Opt. Lett. 17, 577 (1992)).However, only a few layers are possible with a spin coating technique.Norwood et al in the above publication reports only 23 layers.

The preparation of layered structures of polymeric materials bycoextrusion has been used to prepare materials with combinations ofphysical properties. Such materials having three to seven layers arecommercially available. More recently, the development of layermultiplying dies has allowed the preparation of multilayer polymericmaterials with hundreds or even thousands of layers (E. Baer, J. Kerns,and A. Hiltner; “Processing and Properties of Polymer MicrolayeredSystems: NATO-ASI on Structure Development During Polymer Processing,Guimaraes, Portugal, May 17-28, (1999)). The total thickness of thestructured material is controlled by the feed ratio. With thousands oflayers, individual layer thickness down to 30 nanometers or less can beachieved. Recent processing improvements and improvements in themultiplying elements allow layer thickness to be constant within a fewpercent.

Optical properties of nonlinear dyes have led to the development ofmaterials that have a large nonlinear absorption and/or a largenonlinear refraction coefficients (J. S. Shirk, R. G. S. Pong, F. J.Bartoli, A. W. Snow; Appl. Phys. Lett., 63, 1880 (1993)). In thesematerials, the nonlinear response includes contributions from excitedstate absorption, excited state nonlinear refraction and thermalrefraction. Some of these materials are soluble in polymeric materialsthat are suitable for the microlayer extrusion process.

Accordingly, there is a need to develop multilayer structures thatexhibit improved nonlinear optical response.

SUMMARY OF THE INVENTION

The present invention provides a method and materials for fabrication ofa multilayer structure comprising a plurality of at least twoalternating layers (A) and (B) represented by formula (AB)_(x), wherex=2^(n), and n is in the range of from 2 to 15. Layer (A) is comprisedof component (a) and layer (B) is comprised of component (b), where atleast one of components (a) and (b) exhibits nonlinear optical response.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic representation of an arrangement for coextrusionof two components (a) and (b) to form a multilayer structure ofalternating layers (A) and (B), in accordance with the invention.

FIG. 2 shows a series of multiplying elements.

FIG. 3 is a schematic representation of a flow diagram for a three layersystem (A), (B) and (T), where (T) is a tie layer.

FIG. 4 shows the nanosecond transmission apparatus. The sample ismounted on a translation stage near the focus. A1 and A2 are theentrance and exit apertures L1, L2 and L3 are lenses used to focus thelight on the sample film, recollimate it and weakly focus it on thedetector (Det). Ref is the reference detector.

FIG. 5 shows the reflection spectra of 5 mil and 14 mil nanolayeredSAN25/SAN20 films

FIG. 6 shows the Atomic Force Microscopy (AFM) phase image ofnanolayered SAN25+ nonlinear dye/SAN20 film

FIG. 7 shows the reflection spectra of 4096 layer SAN20/SAN25+ nonlineardye films with different layer thickness. In the upper spectrum theaverage layer thickness is 87 nm, in the lower it is 31 nm.

FIG. 8 shows the closed aperture Z-scan of multilayer nonlinear film ofpolymeric material at 532 nm. The film shows a negative nonlinearrefractive index change with incident fluence.

FIG. 9 shows Transmission vs. Energy for a nigrosine dyed nanolayeredfilm at 532 nm. The film had 4096 layers with an average thickness eachof 87 nm.

FIG. 10 shows Open Aperture Z-scan for a leadtetrakis(cumylphenoxy)phthalocyanine (PbPc(PC)₄) dyed multilayer film at532 nm.

FIG. 11 shows reflection spectra of 4096 layerpolycarbonate/polycarbonate+nigrosine dye films with different layerthickness.

FIG. 12 shows reflectivity at 573 nm as a function of distance fromfocus for a 14 mil, 4096 layer, polycarbonate/polycarbonate+nigrosinedye film (lower curve) compared to that for a film where the layers areidentical (upper curve).

FIG. 13 is a schematic representation of a multilayer optical switch inaccordance with the present invention. Initially, the refractive indicesof the different layers are close to being matched, and the sampletransmission is high (A). When the control beam is present (or thesignal beam becomes sufficiently intense), the refractive index of thelayers is not matched. The resulting index modulation makes the materialan effective dielectric mirror (B). The reflectivity increases and thetransmission falls.

FIG. 14 shows the reflectivity as a function of time for a 4096 layersample, in accordance with the present invention, where the alternatelayers consisted of undoped polycarbonate and the same polymercontaining 0.2% (wt/wt) nigrosine. The sample was mounted between glassplates. The film had an average layer thickness of 87 nanometers (nm).

FIG. 15 shows the reflectivity as a function of time for a free standing4096 layer sample, in accordance with the present invention, similar tothat in FIG. 14. The pump beam was a 1.2 picosecond (ps) pulse at timeequal 0 on the graph. The pump energy was about three times that in FIG.14.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The multilayer structure of the present invention is a nonlineardielectric optical material that has a substantial modulation in thenonlinear dielectric constant across the sample. A material with amodulation in the linear dielectric constant is commonly called a“photonic crystal” (J. D. Joannopoulos, R. D. Meade, and J. N. Winn;“Photonic Crystals” (Princeton Univ. Press, (1995)) when the period ofthe modulation is on the order of a wavelength of light. Thus thematerials described here, which possess a modulation in the nonlineardielectric constant across the sample, can be considered as ID nonlinearphotonic crystals. These materials exhibit an intensity dependenttransmission and reflection. They act as nonlinear mirrors and perform avariety of functions including optical switching and optical limiting.

Accordingly, it is an object of the present invention to provide amultilayer structure as nonlinear multilayer 1-D photonic crystal and amethod for the fabrication of same.

In one embodiment of the present invention the multilayer structure ismade of two alternating layers (ABABA . . . ) of two polymeric materialsreferred to as component “(a)” and component “(b)”, respectively,throughout the description.

Materials

One of ordinary skill in the art will readily appreciate that a widevariety of materials can be used to form the multilayer structure of thepresent invention. The components comprising the different layers of themultilayer structure are polymeric materials chosen to have a differencein the index of refraction of the layers preferably on the order of from0 to 10%, including any increments within that range, most preferably onthe order of 0 to 2%. The degree of index matching is chosen to providethe desired initial level of reflectivity and to maximize the change inreflectivity with nonlinear index. By way of example, the preferredindex matching for polycarbonate (PC) with a refractive index n₀=1.583,is for the alternate layers to be matched to within 0.004 with thenonlinear layer having the smaller index. The component comprising thealternating layers are preferably a polymeric material, a polymericcomposite material, an oligomeric material, and/or a polymeric materialcontaining a nonlinear dye. The content of the nonlinear dye in thepolymeric material is preferably in the order of 0.1 to 5 wt %. Further,it is preferred that a good inter-layer adhesion between co-extrudedlayers is exhibited in the multilayer structure to reduce thepossibility of delamination during end use.

The term “polymeric material” as used in the present application denotesa material having a weight average molecular weight (Mw) of at least5,000. Preferably the polymeric material is an organic polymericmaterial. The term “polymeric composite material” as used in the presentapplication denotes a combination of a polymeric material with at leastone more material dispersed therein; the additional material can beanother polymeric material or an inorganic material; examples of suchinorganic materials include inorganic fillers, such as glass, titaniumdioxide and talc; further, the inorganic material may be the form ofparticles, rods, fibers, plates etc. It is preferred that the compositematerial is substantially optically transparent. Accordingly, it ispreferred that the dispersed material is miscible with the polymericmaterials, has a refractive index substantially the same with thepolymeric material or is finely dispersed to avoid light scattering.Such composite materials are a convenient and useful way to control thelinear part of the refractive index in the individual layers. The term“oligomeric material” as used in the present application denotesmaterial with a degree of polymerization (DP) between 10 and 1000. Theterm “nonlinear dye” as used in the present application denotes amaterial whose dielectric constant and hence the refractive index varieswith the incident light intensity and/or the incident light fluence. Theintensity or fluence dependence can be in either or both the real orimaginary part (absorptive part) of the refractive index. The term“nonlinear optical response” of a material, as used in the presentapplication, denotes that the real and/or the imaginary part of therefractive index of the material is a function of the intensity and/orfluence of the incident light. Specifically, either the absorbanceand/or the refractive index varies with the fluence (intensity). For anoptical limiter, a dye with a nonlinear optical response that includesan absorbance that can increase with fluence (intensity) is particularlyuseful. Further, the multilayer structure of the present invention is a1D photonic crystal in the sense that a photonic crystal is a materialhaving a spatially periodic modulation of the refractive index. Further,the term “nanolayer” is used to denote a layer with thickness innanoscale.

Suitable polymeric materials in accordance with the present inventioninclude but are not limited to, polyethylene naphthalate and isomersthereof such as 2,6-, 1,4-, 1,5-, 2,7-, and 2,3-polyethylenenaphthalate; polyalkylene terephthalates such as polyethyleneterephthalate, polybutylene terephthalate, andpoly-1,4-cyclohexanedimethylene terephthalate; polyimides such aspolyacrylic imides; polyetherimides; styrenic polymers such as atactic,isotactic and syndiotactic polystyrene, α-methyl-polystyrene,para-methyl-polystyrene; polycarbonates such asbisphenol-A-polycarbonate (PC); poly(meth)acrylates such aspoly(isobutyl methacrylate), poly(propyl methacrylate), poly(ethylmethacrylate), poly(methyl methacrylate), poly(butyl acrylate) andpoly(methyl acrylate) (the term “(meth)acrylate” is used herein todenote acrylate or methacrylate); cellulose derivatives such as ethylcellulose, cellulose acetate, cellulose propionate, cellulose acetatebutyrate, and cellulose nitrate; polyalkylene polymers such aspolyethylene, polypropylene, polybutylene, polyisobutylene, andpoly(4-methyl)pentene; fluorinated polymers such as perfluoroalkoxyresins, polytetrafluoroethylene, fluorinated ethylene-propylenecopolymers, polyvinylidene fluoride, and polychlorotrifluoroethylene;chlorinated polymers such as polydichlorostyrene, polyvinylidenechloride and polyvinylchloride; polysulfones; polyethersulfones;polyacrylonitrile; polyamides; polyvinylacetate; polyether-amides. Alsosuitable are copolymers such as styrene-acrylonitrile copolymer (SAN),containing between 10 and 50 wt %, preferably between 20 and 40 wt %,acrylonitrile, styrene-ethylene copolymer; andpoly(ethylene-1,4-cyclohexylenedimethylene terephthalate) (PETG). Inaddition, each individual layer may include blends of two or more of theabove-described polymers or copolymers. Preferred polymeric materialsinclude a styrene-acrylonitrile copolymer and a polycarbonate.

Nonlinear dyes can be used to confer nonlinear absorption, nonlinearrefraction or both on the polymeric materials and polymer compositesused in the multilayer samples. Nonlinear dyes can also be used toenhance the nonlinear optical response of polymers with an inherentnonlinear optical response. The nonlinear absorption property isobtained by using nonlinear dyes that exhibit reverse saturableabsorption, sequential two-photon absorption, or two-photon absorptionwith sequential two-photon absorption or reverse saturable absorptionbeing preferred. Nonlinear dyes exhibiting this property includephthalocyanines, naphthalocyanines, porphyrins, organometallic clustercompounds, and fullerenes. Some preferred materials are leadtetrakis(cumylphenoxy)phthalocyanine (PbPc(CP)₄), leadtetrakis(polydimethylsiloxane) phthalocyanine, tetra-tert.-butyl(para-trifluoromethyl phenyl) indium(III) phthalocyanine andbis(trihexylsiloxy)silicon naphthalocyanine. The nonlinear refractionproperty is obtained by using nonlinear dyes or a polymeric materialthat exhibits an intensity dependent refractive index. The intensitydependent refractive index can be obtained by either thermal expansionin a material with a substantial dn/dT (where n is the refractive indexand T is the temperature) by optical pumping to an excited state wherethe excited state has a different refractive index from the groundstate, by a resonant χ⁽³⁾ (where χ⁽³⁾ is the third order susceptibility)where the resonance is provided by two-photon absorption, for example,or by a nonresonant χ⁽³⁾.

The preferred mechanism is thermal or optical pumping. Nonlinear dyesexhibiting these properties include nigrosine, cyanines,phthalocyanines, naphthalocyanines, porphyrins, organometallic clustercompounds, carbon blacks and fullerenes. The host polymeric materialcontributes to the thermal mechanism, so polymeric materials with largedρ/dT (where ρ is the density) are preferred. Preferred host polymericmaterials include polycarbonates, polystyrenes, poly(methyl)methacrylateand polysiloxanes. The thermal nonlinearity is enhanced by theperipheral substituent on the nonlinear dye. For a thermal nonlinearity,nigrosine, and copper tetrakis(cumylphenoxy)phthalocyanine arepreferred; for an optical pumping nonlinearity leadtetrakis(cumylphenoxy)phthalocyanine (PbPc(CP)₄ ), leadtetrakis(polydimethylsiloxane) phthalocyanine or the equivalentbis(trihexylsiloxy)-silicon naphthalocyanines are preferred nonlineardyes.

Suitable examples of polymeric materials with inherent nonlinearresponse include, but are not limited to, polyacetylene, polythiophene,poly(diacetylene), poly(p-phenylene vinylene), poly(thienylene vinylene)and poly(p-phenylene benzobisthiazole).

Fabrication

The 1-D photonic crystal is then fabricated using these materials in amultilayer extrusion technique. The method preferably yields a flexiblelarge film or sheet of multilayer nonlinear dielectric opticalstructure. The thickness of the individual layers is on the order offrom 5 nanometers to 10 micrometers, preferably from 10 nanometers to1000 nanometers, more preferably from 30 nanometers to 200 nanometers.They are engineered to provide reflectivity within a wavelength regionbetween about 200 micrometers and the near UV (350 nanometers). In otherwords, there should be a transmission window somewhere between 200micrometers and 350 nanometers. The term “about” is used in the presentapplication to denote a deviation from the stated value. Preferably, thepolymeric materials used in the alternating layers are transparent inthe above region. The layer thickness can be varied or chirped toprovide variable reflectivity over a broad band of wavelengths andacceptance angles. Preferably, the layers have substantially uniformlayer thickness, where “substantially” is used to denote a deviationwithin 20%.

For simplicity of discussion, the behavior of a two component system isdescribed. In this embodiment of the present invention the multilayerstructure is made of two alternating layers (ABABA . . . ) of twopolymeric materials referred to as component “(a)” and component “(b)”,respectively, throughout the description. The components (a) and (b),may be the same or different and form a multilayer structure representedby formula (AB)_(x), where x=(2)^(n), and n is the number of multiplierelements. At least one of components (a) and (b) exhibits nonlinearoptical response. It should be understood that the multilayer structureof the invention may include additional types of layers. The componentsof the various alternating layers may be the same or different as longas at least one component exhibits nonlinear optical response. Forinstance, a three component structure of alternating layers (ABCABCA . .. ) of components (a), (b) and (c) is represented by (ABC)_(x), where xis as defined above.

In the two-component system described above one of the alternatinglayers (A) comprises component (a) which is a polymeric material with adissolved nonlinear dye and a second alternating layer (B) comprisescomponent (b) which is a polymeric material alone. It is desirable toadjust the composition so that the difference between the linear indexof the layer containing the nonlinear dye and the linear index of thepolymeric material alone is between 0 and 10% including any incrementstherein, preferably between 0 and 2%. The multilayer structure in theabove embodiment is represented by formula (AB)_(x), where x=(2)^(n),and n is the number of multiplier elements.

In the embodiment described above of a two-component multilayerstructure, the 1-D photonic crystal is prepared by microlayercoextrusion of the two polymeric materials. Nanolayers are comprised ofalternating layers of two or more components with individual layerthickness ranging from the microscale to the nanoscale. A typicalmultilayer coextrusion apparatus is illustrated in FIG. 1. The twocomponent (AB) coextrusion system consists of two ¾ inch single screwextruders each connected by a melt pump to a coextrusion feedblock. Thefeedblock for this two component system combines polymeric material (a)and polymeric material (b) in an (AB) layer configuration. The meltpumps control the two melt streams that are combined in the feedblock astwo parallel layers. By adjusting the melt pump speed, the relativelayer thickness, that is, the ratio of A to B, can be varied. From thefeedblock, the melt goes through a series of multiplying elements. Amultiplying element first slices the AB structure vertically, andsubsequently spreads the melt horizontally. The flowing streamsrecombine, doubling the number of layers. An assembly of n multiplierelements produces an extrudate with the layer sequence (AB)_(x) where xis equal to (2)^(n) and n is the number of multiplying elements. It isunderstood by those skilled in the art that the number of extruders usedto fabricate the structure of the invention equals the number ofcomponents. Thus, a three-component multilayer (ABC . . . ), requiresthree extruders.

The multilayer structure of the present invention preferably has atleast 30 layers, including any number of layers within that range.Preferably, the multilayer structure of the present invention has from50 to 10000 layers. Preferably, the multilayer structure is in the formof film or sheet. By altering the relative flow rates or the number oflayers, while keeping the film or sheet thickness constant, theindividual layer thickness can be controlled. The multilayer structurefilm or sheet has an overall thickness ranging from 10 nanometers to1000 mils, preferably from 0.1 mils to 125 mils and any incrementstherein. Further, the multilayer structures may be formed into a numberof articles. The structures may be formed by coextrusion techniquesinitially into films or sheets which may then be post formed. Such postforming operations may include thermoforming, vacuum forming, orpressure forming. Further, through the use of forming dies, themultilayer structures may be formed into a variety of useful shapesincluding profiles, tubes and the like.

Structures exhibiting unique optics can be produced with microlayerprocessing technology. The present inventors have found that layeringimproves the nonlinear optical response of a multilayer structure. Inother words, the larger the number of layering the better the nonlinearoptical response of the multilayer structure. In accordance with thepresent invention, when two materials of differing refractive indicesare extruded into a multilayer structure that has layer thickness ofapproximately ¼ the wavelength of visible light, the material will bereflective. Increasing the number of layers increases the number ofinterfaces, and thus amplifies the reflective response.

In another embodiment of the invention, a third polymeric layer isplaced in the multilayer structure as a tie layer, barrier layer ortoughening layer. A multilayer structure containing a third componentexhibits improved properties such as mechanical properties. Thus, athree component multilayer structure expands the utility of the twocomponent nanolayer structure. When the third polymer layer is a barrierlayer, it is present as a single layer on one or both exterior majorsurfaces of the structure or as an interior layer. For example, suitablebarrier layer materials such as hydrolyzed ethylene vinyl acetate,copolymers of polyvinylidene chloride, nitrile polymers, and nylons maybe used in or on the multilayer body. Suitable adhesive materials suchas maleic anhydride grafted polyolefins may be used to bond such barrierlayer materials to the multilayer structure. Alternatively, a thirdpolymeric layer may be used as a surface or skin layer on one or bothmajor exterior surfaces. The skin layer may serve as scratch resistant,weatherable protective layer, as sacrificial layer or as decorativelayer. Further, such skin layers may be post applied to the structureafter coextrusion. A typical three component system according to theabove embodiment is illustrated in FIG. 3. A tie layer (T) is insertedbetween layer (A) and layer (B) by using a five layer feedblock. Thefive layer melt is sliced, then spread and recombined to give a layersequence (ATBT)_(x)A, where x is equal to (2)^(n) for an assembly of nmultiplier elements. The additional polymeric layer may be a barrierlayer

Nonlinear Response

Thermal changes in the index of refraction are generally largest. Theserequire a nonlinear dye that converts the absorbed energy to heatefficiently and rapidly and a polymeric material host that has a largechange in index or refraction with temperature. Nigrosine is a typicalexample of this class of nonlinear dyes. Another class of materials thatcan be used as the nonlinear dye is a phthalocyanine, a porphyrin and anaphthalocyanine (H. S. Nalwa, and J. S. Shirk, “Nonlinear OpticalProperties of Metallophthalocyanines” in Phthalocyanines: Properties andApplication, C. C. Leznoff and A. B. P. Lever, Eds., VCH Publishers, NewYork, 4, 79 (1996)). Nonlinear dyes of this type are appropriate if theyare substituted at the peripheral or axial positions to providesolubility and compatibility with the polymeric material host. PbPc(CP)₄in a styrene/acrylonitrile copolymer host is an example. These nonlineardyes usually possess a nonlinear absorption as well as a nonlinearrefraction, so the absorption increases with the incident fluence. Theincreasing absorption serves to enhance the thermal nonlinear mechanism.It also makes these materials particularly suitable for use as opticallimiter.

Optical Switches

The nanolayered materials of the present invention can act as opticalswitches. The basic principle for nonlinear reflection using thenanostructured material can be understood from FIG. 13. The opticalswitch consists of alternate layers of a linear polymer and a polymerwhose index of refraction varies with light intensity. Initially, therefractive indices of the different layers are close to being matched,and the sample transmission is high (A). When the control beam ispresent, the refractive index of the layers is not matched. Theresulting index modulation, with a spacing of λ/4, makes the material aneffective dielectric mirror (B). The increased reflectivity will causethe signal beam to be reflected.

These materials can also be self-acting switches. If the signal beambecomes sufficiently intense, it will cause the reflectivity to increaseand the transmission to fall. This property is useful for opticallimiting applications.

The response time of the optical switches, in accordance with thepresent invention, is preferably at least 20 femtosecond, morepreferably on the order of 1 to 1000 picoseconds, and most preferablybetween 10 to 500 picoseconds, including any increments within the aboveranges.

Optical Limiters

In another embodiment of the present invention, the multilayer structureof the can be used as an optical limiter. A material that has themultilayer structure of the present invention will provide a limitingeffect superior to that found in equivalent homogeneous materials. Incurrent optical limiters, nonlinear absorption, nonlinear refraction andnonlinear scattering all are contributing mechanisms. Nonlinearabsorption, where the material absorbance increases with the intensityof the incident light, is a good mechanism to remove light from thetransmitted beam. Nonlinear refraction can be used to deflect or scatterlight out of the transmitted beam, thereby decreasing the devicetransmission. When the nonlinear material has a refractive index thatdepends on the light intensity or fluence, the intensity distributionacross the beam generates a refractive index variation in the nonlinearmaterial that behaves as a lens with strong aberrations. This lens willdeflect some of the light into the wings of the transmitted beam wherean exit aperture blocks it. This serves to limit the energy in thetransmitted beam at high input fluences.

All these optical limiting mechanisms will be effective when the limitermaterial possesses the multilayer structure of the present invention. Inaddition, the multilayer structures will provide an optical switchingmechanism, as described above, that will contribute to and enhance theoptical limiting. Further, the multilayer structure will provideenhanced nonlinear absorption, since the internal reflections inducedwithin the multilayer structure will increase the effective path length,and reduce the transmission.

Following is a comparison of the present invention with the structure ofthe Norwood et al. publication (R. A. Norwood et al.; Opt. Lett. 17, 577(1992)). The Norwood et al structure used 23 layers of a copolymer ofsilicon naphthalocyanine/methyl methacrylate alternating with methylmethacrylate. The layers were constructed via spin coating. Themechanism of the nonlinear response was saturable absorption. Thismechanism leads to a strong absorption at the operating wavelength.Accordingly:

1. The highly absorbing nonlinear layer limits the number of layers thatcan be used. This makes the structure much more susceptible to opticaldamage. Damage was reported at 15-20 MW/cm² for the Norwood structure.In contrast, the multilayer polymer of the present invention reflectorscan sustain greater than 500 MW/cm².

2. The limited number of layers possible means the Norwood et al devicecan have only a narrow band reflectivity. The small number of layersthat are possible means that this device cannot achieve a largereflectivity over more than about 20-30 nm. Multilayer samples canexhibit a reflectivity greater than 500 nm.

3. The Norwood device gives an increase in transmission and a decreasein reflection with increasing intensity. This response is not useful asa transmission optical limiter. Further, the narrow band reflectivityand the strong absorption at the reflecting wavelength are not useful ina limiter. Multilayer samples show an increase in reflectivity and adecrease in transmission with increasing incident intensity atwavelengths where the low intensity transmission can be greater than80%.

4. The Norwood et al structure as an optical switch has large absorptionlosses and the peak of only 20% reflectivity at the operatingwavelength. By contrast, the multilayer structure of the presentinvention, operating as optical switches, have greater than 95%reflectivity with absorption losses of less than 1%. The latter makes amore efficient optical switch that can be operated at much higher rates.

5. The extrusion technique is capable of making much larger dimensionedmultilayer structures of a much wider variety of materials. It alsoallows the easy fabrication of many more layers than the spin coatingtechnique. Extrusion also permits faster and more economical fabricationthan stepwise spin coating. Since spin coating requires that thealternate layers be relatively insoluble, it is not feasible to preparemultilayer structures with polymeric materials containing a soluble dye.

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples which are providedherein for purposes of illustration only and are not intended to belimiting unless otherwise specified.

EXAMPLES

Non-linear dielectric optical structures were made by coextruding 4096nanolayered sheets of alternating dyed and undyedpoly(styrene-co-acrylonitrile). Base refractive indices were tailored bychoosing poly(styrene-acrylonitrile) copolymer (SAN) materials withdiffering acrylonitrile content. Layer thickness in the range of 100 nmwere processsed fabricating 1-D photonic crystals.

System:2 component.

Number Of Layers: 4096

Composition Materials 50/50 0/100 1 SAN 20/SAN 25 + 5,14 mils — 0.2 wt %Nigrosine Dye 2 SAN 20/SAN 25 + 14 mils — 1 wt % Lead Dye¹ 3 PC/PC +5,14,20 mils 20 mils 0.2 wt % Nigrosine Dye 4 PC/PC + 5,14 mils — 1 wt %Lead Dye¹ ¹lead tetrakis(cumylphenoxy)phthalocyanine SAN 20 denotes acopolymer of styrene-acrylonitrile containing 20 wt % of acrylonitrile,TYRIL 100 manufactured by Dow; SAN 25 denotes a copolymer ofstyrene-acrylonitrile containing 25 wt % of acrylonitrile, TYRIL 990manufactured by Dow. The polycarbonate was CALIBRE 200-14 manufacturedby Dow.

Details of the Mixing Procedure(Polymer-Dye)

A counter rotating intermeshing twin screw extruder was used for mixingthe polymeric material and the nonlinear dye.

Mixing Temperature Mixing Speed Materials (° C.) (rpm) 1 SAN + 0.2 wt %Nigrosine Dye 230 25 2 SAN + 1 wt % Lead Dye¹ 220 25 3 PC + 0.2 wt %Nigrosine Dye 257 21 4 PC + wt % Lead Dye¹ 257 21 ¹leadtetrakis(cumylphenoxy)phthalocyanine SAN 20 denotes a copolymer ofstyrene-acrylonitrile containing 20 wt % of acrylonitrile; SAN 25denotes a copolymer of styrene-acrylonitrile containing 25 wt % ofacrylonitrile.

Details of Multilayer Coextrusion

Extruders

Make—KILLION Extruders Inc.

Size—¾″

L/D ratio—24:1

Melt Pumps

ZENITH Pumps Inc.

Capacity—1.2 cc/hr

Multipliers

Long multipliers were used.

# of multipliers—11

Die

A 3″ die was used.

Processing Conditions

1. SAN 20/SAN25 + 0.2 wt % Nigrosine Dye Temperature (° C.) Barrel Zone#1 200 Barrel Zone #2 220 Barrel Zone #3 230 Clamp 230 Adapter 230 Pump230 Multipliers 210 Exit Die 230 Extruder 1 Extruder 2 Screw Speed (rpm)35 24 Pump Speed (rpm) 20 20 2. SAN 20/SAN 25 + 1 wt % Lead Dye¹Temperature (° C.) Barrel Zone #1 230 Barrel Zone #2 250 Barrel Zone #3265 Clamp 265 Adapter 265 Pump 265 Multipliers 220 Exit Die 240 Extruder1 Extruder 2 Screw Speed (rpm) 25 31 Pump Speed (rpm) 20 20 ¹leadtetrakis(cumylphenoxy)phthalocyanine SAN 20 denotes a copolymer ofstyrene-acrylonitrile containing 20 wt % of acrylonitrile; SAN 25denotes a copolymer of styrene-acrylonitrile containing 25 wt % ofacrylonitrile.

3. PC/PC + 0.2 wt % Nigrosine Dye Temperature (° C.) Barrel Zone #1 220Barrel Zone #2 250 Barrel Zone #3 270 Clamp 270 Adapter 270 Pump 270Multipliers 210 Exit Die 220 Extruder 1 Extruder 2 Screw Speed (rpm) 2732 Pump Speed (rpm) 17 17 4. PC/PC + 1 wt % Lead Dye¹ Temperature (° C.)Barrel Zone #1 208 Barrel Zone #2 242 Barrel Zone #3 253 Clamp 253Adapter 253 Pump 253 Multipliers 190 Exit Die 200 Extruder 1 Extruder 2Screw Speed (rpm) 3.5 3.8 Pump Speed (rpm) 7.0 7.0 ¹leadtetrakis(cumylphenoxy)phthalocyanine

A description of the linear and nonlinear optical properties of somenanolayer polymeric structures fabricated by the extrusion methodfollows. Further, it was shown that the multilayer films exhibit abroadband reflectivity in the visible with relatively small indexdifferences between the layers. It was then shown that the nonlinearnanolayered materials of the present invention exhibited a transmissionand reflectivity that varied with the intensity or fluence of anincident beam. The layered film behaves as a nonlinear ID photoniccrystal.

Experimental Apparatus

The samples of the ID photonic materials and control samples were cutdirectly from the extruded material. Some samples were mounted betweenmicroscope slides using an optical cement. Mounting reduced scatteringfrom the surface of the extruded polymeric materials. Absorption spectraof each of the samples were recorded on a PERKIN-ELMER LAMBDA 9spectrophotometer. Absorption spectra of small regions of the sampleswere recorded using an OCEAN OPTICS fiber optic spectrometer. Reflectionspectra were recorded using the fiber optics spectrometer with areflectance probe.

The nanosecond transmission and reflection experiments were performedusing the apparatus shown in FIG. 4. The samples were mounted on atranslation stage near the focus of a laser. The laser source for thenanosecond experiments was an optical parametric oscillator (OPO) pumpedby the third harmonic of a Nd/YAG laser. The pulse width was 2.5nanoseconds. Some of the nanosecond experiments at 532 nm used a doubledNd/YAG laser with an 8 nanosecond pulse width. In both cases, the inputbeam was spatially filtered to give a spatial profile that typicallyshowed a greater than 96% correlation with a gaussian profile. The laserintensity was controlled by several wave plate/polarizer combinations inseries.

The experiments at low energies were conducted at a 10 Hz repetitionrate. For incident fluences above 10 mJ/cm², the repetition rate wasreduced to 0.5 Hz in order to reduce any effect due to persistentheating.

Two different sets of focusing optics were used. In the first, the inputbeam was focused using approximately f/45 optics. The focal spot size,f/number, and the beam quality were determined from knife edge scans atseveral positions along the beam path near the focus. The measured M²increased from 1.1 at 530 nm to 1.3 at 610 nm. A diffraction limitedgaussian beam would have M²=1. The measured focal spot size was withinabout 10% of that expected for a gaussian beam between 530 nm and 610nm. The second set of optics was f/S focusing optics. The input laserbeam was expanded so that only the first aperture transmitted thecentral 10% of the beam. This gives the beam an approximately flat topintensity profile. The lens L1 was a corrected multiplet, which focusedthe light to a spot with a measured beam radius of 2.5±0.1 μm at 532 nm.This was close to the expected radius for a diffraction-limited spotsize, which is 2.2 μm. With the OPO as a source, the beam radius wasmeasured to be 2.6±0.1 μm at 550 nm.

In both cases, the light passing through the sample was recollimated byL2 and focused by lens L3 onto the detector. With no exit aperture (A2),lens L2 in the second optics set provided approximately f/0.8 collectionoptics. The film was mounted on a translation stage and translatedthrough the focus for the Z-scan experiments. For nonlinear transmissionmeasurements, the position was adjusted about the focus to give thesmallest transmitted energy for incident energies near the limitingthreshold.

In the reflection experiments, the sample was rotated so that angle ofincidence was about 10°. A small pickoff mirror was used to directreflected light to a third detector next to the reference detector.

Optical switching measurements were made by measuring the reflectivityof a multilayer sample as a function of time after a separate pump beamwas incident on the sample. The picosecond (ps), time resolved,experiments were performed using a dye laser that is synchronouslypumped by the second harmonic of a CW mode-locked Nd: YAG laser. The dyelaser output is amplified in a three-stage dye amplifier pumped usingthe second harmonic of a regenerative Nd: YAG amplifier seeded with thefundamental of the mode-locked Nd: YAG laser. The 10 Hz output of thelaser system provides 1.2 ps FWHM pulses with energies up to 1 mJ. Itwas tuned near 590 nm for these experiments. The beam is split into twoor three beams that can be used as pump and probe beams. The intensityof the beams is varied using waveplate/polarizer combinations. Thetiming between the arrival of the beams at the sample is achieved byvariable optical delay lines. The apparatus is modified from adegenerate four-wave nixing apparatus that has been described in detailin Shirk et al (Shirk, J. S.; Lindle, J. R.; Bartoli, F. J.; Boyle, M.E., J. Phys. Chem., 96, 5847 (1992)) and Flom et al. (Flom, S. R.; Pong,R. G. S.; Bartoli, F. J.; Kafafi, Z. H. Phys. Rev. B, 46, 15598 (1992))both of which are incorporated herein by reference.

The reflectivity measurements were made by overlapping a variableintensity pump beam with a probe beam at the sample. The probe beam wasnormal to the polymer surface. The pump beam was incident at 13° fromnormal to the surface of the film. The reflectivity of the film wasmeasured with a detector at the specular reflection angle Timeresolution is obtained by varying the optical path of the pump beam.Additional experiments were performed with the pump beam normal to thesurface of the multilayer sample and the probe beam at 13° from normal.

Results

Polycarbonate/poly(methyl methacrylate) ID photonic crystals

Nanolayered films with alternating polycarbonate (PC) layers andpoly(methyl methacrylate) (PMMA) layers with equal thickness wereprepared. These had from 32 to 4096 layers and the individual layerthickness varied from 12 nm to several microns. These film samples wereup to 12 inches wide and several feet long. The refractive index of PCis about 1.58 and that of PMMA is about 1.49. This index contrast islarge enough so that films with a layer thickness between 65 nm and 115nm exhibit a strong visible reflection. Qualitatively, those films wherethe band gap fell in visible showed a broad, strong, reflectivity in thevisible that was obvious on visual inspection. These films had a silveryappearance. Those films where the layers were much thinner or thickerappeared transparent and showed only the Fresnel reflectivity of a fewpercent.

Styrene-Acrylonitrile Copolymer 1D Photonic Crystals

Several nonlinear nanolayered polymeric films were fabricated. The firstwere made of SAN25, a styrene-acrylonitrile copolymer with 25%acrylonitrile. A nonlinear response was introduced into the alternatelayers of SAN25 by dissolving a nonlinear dye in the polymeric material.The nonlinear dyes used were PbPc(CP)₄ and nigrosine. The nigrosine hasa broad absorption in the visible and an excited state that relaxes onthe sub-picosecond time scale with the conversion of the absorbed energyinto heat. The resulting rise in temperature caused a thermal change inthe refractive index of the host polymeric material. The nigrosine dyedSAN is an example of a thermal refractive nonlinear material. Multilayerfilms consisting of layers of SAN25 doped with a nonlinear dyealternating with an undyed SAN20 polymer (styrene-acrylonitrile with 20%acrylonitrile) layer were also fabricated. The refractive index of theSAN20 was about 0.0045 larger than that of SAN25. Dissolving nigrosinedye in the SAN25 polymer raised the refractive index by approximately0.003. Thus using SAN20 in the linear layers gave a better indexmatching with the dyed layer of the film.

Linear Optical Properties of the SAN Films

One of the control samples had alternate layers of SAN20 and SAN25 withno dye in either layer. The index difference between the layers wasabout 0.003. This nanolayered film illustrates the broadbandreflectivity that can be achieved with small index differences. FIG. 5shows the reflection spectrum of two of these materials, The one labeled14 mil had 4096 layers with an average thickness of 87 nm and thatlabeled 5 mil had 4096 layers with an average thickness of 31 nm. Thefilm with 87 nm layers had a first order band gap in the visible., Itshows a strong broad reflection in this region. The film with 31 nmlayers showed a flat reflection spectrum. The first order band gap forthis film occurs near 197 nm, deep into the UV. The narrow spikes on thereflection spectrum of the 87 nm spacing (14 mil) arise because of thedistribution of the layer thickness across the sample.

A similar SAN25/SAN20 multilayered film was carefully cleavedperpendicular to the plane of the film. The thickness of the individuallayers was then measured by atomic force microscopy (AFM). The AFM imageis shown in FIG. 6. This figure shows the layer structure clearly. Italso shows that there is a distribution of layer thickness across thesample. In this film the layer thickness distribution is qualitativelyconsistent with the width of the band gap observed in the reflectionspectrum (FIG. 5). Relatively broad band gaps are essential for opticallimiter applications. For other optical applications it will bedesirable to adjust the fabrication technique to reduce the band gapwidth.

The reflection spectrum of multilayer films where the SAN25 layers weredyed with nigrosine is shown in FIG. 7. The films have approximately thesame layer thickness as the films shown in FIG. 5. The film with an 87nm average layer thickness showed a similar band gap to the undyed filmbut with a lower reflectivity in the band gap. The nigrosine dyeincreases the index of the SAN25 layer so the refractive index contrastwas smaller.

Nonlinear Optical Studies of the SAN Films

Nanosecond nonlinear transmission and Z-scan experiments were performedon a multilayer film consisting of alternate layers of an undyed SANpolymer and the same polymer containing 0.1% (wt/wt) nigrosine. The filmhad 4096 layers and the average thickness of the layers was 93 nm. Theopen aperture Z-scan showed no variation in transmission with position,as expected, since this film has no nonlinear absorption. FIG. 8 showsthe transmission of this film for a closed aperture (40% transmitting)Z-scan. This demonstrates a nonlinear refraction in this sample. Theshape of the scan indicates a decrease in refractive index with fluence.This is the sign expected for the thermal nonlinearity in the dyedlayers.

The relative transmission of this film as a function of incident energyin an f/5 optical limiter is shown in FIG. 9. In this experiment, thelaser beam was brought to a focus at the center of the multilayer film.The transmission was approximately constant until a threshold wasreached. After the threshold, the transmission dropped rapidly to atransmission below 25%. The experiment shown in FIG. 9 was performedusing a 0.5 Hz laser repetition rate. The same transmission changes wereobserved with a 10 Hz repetition rate. This means the transmissionchanges are not due to persistent local heating of the sample. However,refractive index changes in the polymeric material with a relaxationtime of greater than 2 seconds can contribute to the observed response.

Another 1D nonlinear photonic crystal film consisted of alternate layersof an undyed SAN25 polymer and the same polymer with 0.5% (wt/wt) leadtetrakis(cumylphenoxy)phthalocyanine (PbPc(CP)₄). It was a 4096 layerfilm with an average layer thickness of 93 nm. The leadtetrakis(cumylphenoxy)phthalocyanine dye was substantially molecularlydispersed in the polymeric material. An open aperture Z-scan recorded asa function of increasing energy on this sample in an f/5 optical systemat 532 nm was shown in FIG. 10. This figure shows transmission as afunction of film position at increasing input fluences. This shows thatthis multilayer film exhibits a strong nonlinear absorption. This is inaddition to the nonlinear refraction that appears in the nigrosine dyedsample. At the highest energy shown, an additional drop in transmissionis seen that is consistent with a nonlinear refraction contribution.

Polycarbonate Nonlinear 1D Photonic Crystals

Several nonlinear nanolayered polymeric films were fabricated using apolycarbonate host. The nonlinear response was introduced into thealternate layers by dissolving nigrosine or leadtetrakis(cumylphenoxy)phthalocyanine (PbPc(CP)₄) dye in the polymericmaterial used for those layers. In these films, the same polymericmaterial was used for the dyed and undyed layer. The nonlinear dyecauses a slight increase in the refractive index of the dyed layer, soindex of refraction of the dyed layers was slightly greater than that ofthe undyed layer. This led to a small linear reflectivity of the filmsin the band gap. This is shown in FIG. 11 which gives the reflectionspectrum of two multilayer films consisting of alternate layers of anundyed polycarbonate and the same polymeric material with 0.2% (wt/wt)nigrosine. In this figure, the reflectivity of a 14 mil film with anaverage layer thickness of 87 nm shows a broad reflectivity in the 500nm to 900 nm region. This reflectivity was absent in the 5 mil film witha layer thickness of 31 nm.

Nonlinear Optical Studies of the Polycarbonate 1D Photonic Crystal Films

Nanosecond nonlinear transmission and Z-scan transmission experimentswere performed on the first multilayer film shown in FIG. 11. Itconsisted of alternate layers of an undyed polycarbonate and the samepolymeric material with 0.2% (wt/wt) nigrosine. The film had 4096 layersand an average layer thickness of 87 nm. The nonlinear transmission ofthis film was compared to a similar film in which all the layers weredyed. In the latter film there was no modulation in the nonlinearproperties across the sample.

In order to measure the nonlinear reflectivity, the sample was mountedon a translation stage and positioned near the focus of the f/45 opticalsystem. The film was translated through the focus and the reflectivitywas measured as a function of distance from focus. This is a convenientway to measure the fluence or intensity dependence of the reflectivitysince the intensity and fluence of the beam vary with the distance fromthe focus. The result is shown in the lower plot in FIG. 12. There isabout a 10% drop in reflectivity as the sample comes to the focus. Thiswas expected since the dyed layers initially had a larger index than theundyed layers and the change in index of refraction with fluence isnegative. The reflectivity should decrease and the transmission shouldrise as the layers came closer to being index matched. In thisexperiment, the transmission of the multilayer film did increase withincident fluence.

Two control experiments were performed. The upper plot in FIG. 12 showsthe reflectivity as a function of position for the film where all thelayers of the film contained the nonlinear dye. In this uniformly dyedfilm, the reflection was not position or fluence dependent. In thisfilm, the index remained uniform throughout the film at all fluences.This confirms that reflectivity in the first film arises because of thealternate nonlinear layers.

In addition we studied the nonlinear reflection from a film consistingof alternate layers of an undyed polycarbonate and the same polymericmaterial with 0.2% (wt/wt) nigrosine that had 4096 layers and averagethickness of the layers of 124 nm. In the latter film, a band gap near800 nm is expected. No intensity dependent reflectivity was observed at573 nm. The nonlinear reflectivity was observed only in the band gap ofthe photonic crystal. This shows a reversible nonlinear reflectivitywithin the band gap in this layered film. The nanolayered film behavesas a nonlinear photonic crystal.

Optical switching and the Response Time of the Reflectivity Changes.

Optical switching was demonstrated by measuring the reflectivity of amultilayer sample, in accordance with the present invention, after ashort pulse pump (control) beam was incident on the sample. Themultilayer sample consisted of alternate layers of an undopedpolycarbonate and the same polymer with 0.2% (wt/wt) nigrosine. The filmhad 4096 layers and an average layer thickness of 87 nm. The responsetime of the reflectivity was measured by studying the reflectivity as afunction of time.

The reflectivity of a multilayer sample to a probe (signal) beam at 590nm is shown in FIG. 14 as a function of time after a 1.2 picosecond pumplaser is incident on the layered sample. The reflectivity decreases witha response time of 300 to 400 picoseconds. The decrease in reflectivityoccurred because the dyed layers initially had a larger index than theundyed layers and the change in index of refraction with fluence isnegative. As the layers came closer to being index matched, thereflectivity decreased.

The delay in the change in reflectivity can be easily understood. Inthis particular nanolayered material, the dominant source of therefractive index change is due to the thermal expansion of the absorbinglayer. The dynamics of the generation of the reflectivity is thenanalogous to the formation of a thermal grating in a dynamic gratingexperiment as discussed in Eichler et al (H. J. Eichler, P. Gunther, D.W. Pohl; Laser-induced Dynamic Gratings; Springer-Verlag, Berlin, N.Y.(1986)) which is incorporated herein by reference. Absorption of thepump light causes a temperature rise in the polymer layers containingthe dye. This occurs within the 1.2 picosecond pulse width of the pumplaser. The temperature rise causes the generation of acoustic waveswithin the sample. The acoustic waves are damped via acoustic absorptionto leave a static modulation in the density across the sample. This isthe “thermal grating” in dynamic grating experiments. In the layeredsamples, with a distribution of layer thickness, there is a distributionof periods for the acoustic waves. The observed reflectivity rises asthe acoustic waves damp out to leave a static variation in therefractive index across the sample.

This demonstrates that a multilayer nonlinear photonic crystal can workas an optical switch. The response time illustrated is on the order of afew hundred picoseconds. Faster response times can be achieved by othernonlinear mechanisms or by using a higher intensity pump beam toinitiate the optical switching. This is illustrated in FIG. 15 where aresponse time of about 10 picoseconds is achieved by a higher energypump beam. A response time of 2 to 10 picoseconds is expected for othernonlinear mechanisms, e.g. an excited state nonlinearity.

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein

What is claimed is:
 1. A multilayer structure comprising, a plurality ofat least two alternating layers A and B represented by formula (AB)_(x),where x=2^(n), and n is in the range of from 4 to 15; wherein layer A iscomprised of component (a) and layer B is comprised of component (b);wherein at least one of components (a) and (b) is an organic polymericmaterial containing a nonlinear dye and exhibiting nonlinear opticalresponse; and wherein said organic polymeric material is selected fromthe group consisting of polyethylene naphthalate, isomers ofpolyethylene naphthalate, polyalkylene terephthalates, polyetherimides,a styrenic polymer, a polycarbonate, a poly(meth)acrylate, a cellulosederivative, a polyalkylene polymer, a fluorinated polymer, a chlorinatedpolymer, a polyethersulfone, polyacrylonitrile, a polyamide,polyvinylacetate, a polyetheramide, a styrene-acrylonitrile copolymercontaining between 10 and 50 wt % acrylonitrile, a styrene-ethylenecopolymer, poly(ethylene-1,4-cyclohexylenedimethylene terephthalate) andblends thereof.
 2. The structure of claim 1, comprising a plurality ofat least three alternating layers A, B and C, represented by formula(ABC)_(X), wherein layer A is comprised of component (a), layer B iscomprised of component (b) and layer C is comprised of component (c);and wherein said components (a), (b) and (c) may be the same ordifferent, provided that at least one of the components (a), (b) and (c)exhibits nonlinear optical response.
 3. The multilayer structure ofclaim 1, wherein the difference in the refractive index of component (a)and component (b) is in the range of 0 to 10%.
 4. The multilayerstructure of claim 1, wherein components (a) and (b) have a transmissionwindow within the range of about 200 micrometers and about 350nanometers.
 5. The multilayer structure of claim 1, wherein at least oneof the components (a) and (b) is a polymeric composite material.
 6. Themultilayer structure of claim 1, wherein said nonlinear dye affectschange in the refractive index by thermal change.
 7. The multilayerstructure of claim 1, wherein said nonlinear dye affects change in therefractive index by optical pumping.
 8. The multilayer structure ofclaim 1, wherein said nonlinear dye is selected from the groupconsisting of a phthalocyanine, a naphthalocyanine, a porphyrin, anorganometallic cluster compound, a fullerene, leadtetrakis(cumylphenoxy)phthalocyanine, leadtetrakis(polydimethylsiloxane) phthalocyanine,tetra-tert-butyl(p-trifluoromethyl phenyl) indium(III) phthalocyanineand bis(trihexylsiloxy)silicon naphthalocyanine.
 9. The multilayerstructure of claim 8, wherein said phthalocyanine is selected from thegroup consisting of lead tetrakis(cumylphenoxy)phthalocyanine, leadtetrakis(polydimethylsiloxane) phthalocyanine, andtetra-tert.-butyl(para-trifluoromethyl phenyl) indium(III)phthalocyanine.
 10. The multilayer structure of claim 1, wherein saidmultilayer structure contains at least 30 layers.
 11. The multilayerstructure of claim 1, wherein the thickness of each layer is in theorder of from 5 nanometers to 10 micrometers.
 12. The multilayerstructure of claim 1, which includes a tie layer (T) between layer A andlayer B; said multilayer structure represented by formula (ATBT)_(x)A,where x=2^(n) and n is the number of multiplier elements.
 13. Themultilayer structure of claim 1, which includes a barrier layer.
 14. Themultilayer structure of claim 1, which includes a surface layer on atleast one major surface thereof.
 15. The multilayer structure of claim1, wherein said multilayer structure is a film or a sheet.
 16. Themultilayer structure of claim 1, wherein said multilayer structure is anoptical limiter.
 17. The multilayer structure of claim 1, wherein saidmultilayer structure is an optical switch.
 18. The multilayer structureof claim 17, wherein the response time of said optical switch is atleast 20 femtosecond.
 19. A method for forming the multilayer structureof claim 1, comprising extruding component (a) in an extruder (A) toform a melt stream (A) and component (b) in an extruder (B) to form amelt stream (B); combining melt stream (A) with melt stream (B) in afeedblock to form parallel layers (A) and (B); advancing said parallellayers through a series of multiplying elements (n) to form themultilayer structure.
 20. The multilayer structure of claim 1, whereinsaid organic polymeric material is polyethylene naphtalate.
 21. Themultilayer structure of claim 1, wherein said organic polymeric materialis polyalkylene terephthalate.
 22. The multilayer structure of claim 1,wherein said organic polymeric material is a polyetherimide.
 23. Themultilayer structure of claim 1, wherein said organic polymeric materialis a styrenic polymer.
 24. The multilayer structure of claim 23, whereinsaid styrenic polymer is selected from the group consisting of atacticpolystyrene, isotactic polystyrene, syndiotactic polystyrene,a-methyl-polystyrene and a para-methyl-polystyrene.
 25. The multilayerstructure of claim 1, wherein said organic polymeric material is apolycarbonate.
 26. The multilayer structure of claim 25, wherein saidpolycarbonate is bisphenol-A-polycarbonate.
 27. The multilayer structureof claim 1, wherein said organic polymeric material is apoly(methyl)methacrylate.
 28. The multilayer structure of claim 1,wherein said organic polymeric material is a cellulose derivative. 29.The multilayer structure of claim 28, wherein said cellulose derivativeis selected from the group consisting of ethyl cellulose, celluloseacetate, cellulose propionate, cellulose acetate butyrate and cellulosenitrate.
 30. The multilayer structure of claim 1, wherein said organicpolymeric material is a polyalkylene polymer.
 31. The multilayerstructure of claim 30, wherein said polyalkylene polymer is selectedfrom the group consisting of polyethylene, polypropylene, polybutylene,polyisobutylene and poly(4-methyl)pentene.
 32. The multilayer structureof claim 1, wherein said organic polymeric material is a fluorinatedpolymer.
 33. The multilayer structure of claim 32, wherein saidfluorinated polymer is selected from the group consisting ofperfluoroalkoxy resins, polytetrafluoroethylene, fluorinatedethylene-propylene copolymers and polyvinylidene fluoride.
 34. Themultilayer structure of claim 1, wherein said organic polymeric materialis a chlorinated polymer.
 35. The multilayer structure of claim 1,wherein said organic polymeric material is a polyethersulfone.
 36. Themultilayer structure of claim 1, wherein said organic polymeric materialis polyacrylonitrile.
 37. The multilayer structure of claim 1, whereinsaid organic polymeric material is a polyamide.
 38. The multilayerstructure of claim 1, wherein said organic polymeric material ispolyvinylacetate.
 39. The multilayer structure of claim 1, wherein saidorganic polymeric material is a polyetheramide.
 40. The multilayerstructure of claim 1, wherein said organic polymeric material is astyrene-acrylonitrile copolymer containing between 10 and 50 wt %acrylonitrile.
 41. The multilayer structure of claim 1, wherein saidorganic polymeric material is a styrene-ethylene copolymer.
 42. Themultilayer structure of claim 1, wherein said organic polymeric materialis poly(ethylene-1, 4-cyclohexylenedimethylene terephthalate.
 43. Themultilayer structure of claim 1, wherein said dye is a phthalocyanine.44. The multilayer structure of claim 1, wherein said dye isnaphthalocynine.
 45. The multilayer structure of claim 1, wherein saiddye is a porphyrin.
 46. The multilayer structure of claim 1, whereinsaid dye is an organometallic cluster compound.
 47. The multilayerstructure of claim 1, wherein said dye is a fullerene.
 48. Themultilayer structure of claim 1, wherein said dye is leadtetrakis(cumylphenoxy)phthalocyanine.
 49. The multilayer structure ofclaim 1, wherein said dye is tetra-tert-butyl(p-trifluoromethyl phenyl)indium(III).
 50. The multilayer structure of claim 1, wherein said dyeis bis(trihexylsiloxy)silicon naphthalocyanine.
 51. A multilayerstructure comprising, a plurality of at least two alternating layers Aand B represented by formula (AB)_(x), where x=2^(n), and n is in therange of from 4 to 15; wherein layer A is comprised of component (a) andlayer B is comprised of component (b); wherein at least one ofcomponents (a) and (b) exhibits nonlinear optical response; and whereinsaid component (a) is an oligomeric material (A) and said component (b)is an oligomeric material (A) containing a nonlinear dye.
 52. Amultilayer structure comprising, a plurality of at least two alternatinglayers A and B represented by formula (AB)_(x), where x=2^(n), and n isin the range of from 4 to 15; wherein layer A is comprised of component(a) and layer B is comprised of component (b); wherein at least one ofcomponents (a) and (b) exhibits nonlinear optical response; and whereinthe difference in the refractive index of component (a) and component(b) is
 0. 53. A multilayer structure comprising, a plurality of at leasttwo alternating layers A and B represented by formula (AB)_(x), wherex=2^(n), and n is in the range of from 4 to 15; wherein layer A iscomprised of component (a) and layer B is comprised of component (b);wherein at least one of components (a) and (b) is an organic polymericmaterial containing a nonlinear dye and exhibiting nonlinear opticalresponse; and wherein said component (a) is a styrene-acrylonitrilecopolymer containing 20 wt % of acrylonitrile and component (b) is astyrene-acrylonitrile copolymer containing 25 wt % of acrylonitrile.